JPH11217689A - Copper electroplating solution and copper electroplating method using the solution - Google Patents
Copper electroplating solution and copper electroplating method using the solutionInfo
- Publication number
- JPH11217689A JPH11217689A JP1846898A JP1846898A JPH11217689A JP H11217689 A JPH11217689 A JP H11217689A JP 1846898 A JP1846898 A JP 1846898A JP 1846898 A JP1846898 A JP 1846898A JP H11217689 A JPH11217689 A JP H11217689A
- Authority
- JP
- Japan
- Prior art keywords
- plating
- solution
- copper
- plating solution
- sulfate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 37
- 229910052802 copper Inorganic materials 0.000 title claims description 37
- 239000010949 copper Substances 0.000 title claims description 37
- 238000000034 method Methods 0.000 title claims description 15
- 238000009713 electroplating Methods 0.000 title description 3
- 238000007747 plating Methods 0.000 claims abstract description 89
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 13
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 11
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 11
- 229960003330 pentetic acid Drugs 0.000 claims abstract description 11
- BNZCDZDLTIHJAC-UHFFFAOYSA-N 2-azaniumylethylazanium;sulfate Chemical compound NCC[NH3+].OS([O-])(=O)=O BNZCDZDLTIHJAC-UHFFFAOYSA-N 0.000 claims abstract description 10
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 6
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 6
- 239000003002 pH adjusting agent Substances 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- KLOIYEQEVSIOOO-UHFFFAOYSA-N carbocromen Chemical group CC1=C(CCN(CC)CC)C(=O)OC2=CC(OCC(=O)OCC)=CC=C21 KLOIYEQEVSIOOO-UHFFFAOYSA-N 0.000 claims description 4
- 239000008139 complexing agent Substances 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 230000008961 swelling Effects 0.000 abstract description 10
- 230000007935 neutral effect Effects 0.000 abstract description 4
- 229910021529 ammonia Inorganic materials 0.000 abstract description 3
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 abstract 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 abstract 1
- KCQUJORJVXQRST-UHFFFAOYSA-N acetic acid;ethane-1,2-diamine Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCN KCQUJORJVXQRST-UHFFFAOYSA-N 0.000 abstract 1
- 230000002378 acidificating effect Effects 0.000 description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000006259 organic additive Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000004886 process control Methods 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、プリント配線板等
の電気・電子機器部品用あるいはウエハー配線バンプ形
成用の銅めっき液に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a copper plating solution for electric / electronic device parts such as a printed wiring board or for forming a wiring bump on a wafer.
【０００２】[0002]
【従来の技術】従来より銅めっきは、電気・電子機器部
品製造に広く用いられており、例えばプリント配線板製
造での配線回路の形成即ちパターンめっきやスルーホー
ルめっき等を行う場合にも使用されている。このプリン
ト配線板製造における銅めっき処理方法としては電気め
っきが知られており、そのめっき液種類は硫酸銅系の強
酸性めっき液とシアン化銅又はピロリン酸銅系のアルカ
リ性めっき液のものに大別される。2. Description of the Related Art Conventionally, copper plating has been widely used in the production of electric and electronic equipment parts, and is also used, for example, in the formation of wiring circuits in the production of printed wiring boards, that is, in the case of performing pattern plating, through-hole plating, and the like. ing. Electroplating is known as a copper plating method in the manufacture of printed wiring boards, and the types of plating solutions are broadly classified into those of copper sulfate-based strongly acidic plating solutions and copper cyanide or copper pyrophosphate-based alkaline plating solutions. Separated.
【０００３】[0003]
【発明が解決しようとする課題】このような従来の強酸
性或いはアルカリ性のめっき液を用いてプリント配線板
等に銅めっき処理を行うと、そのプリント配線板に予め
塗布されたレジスト（感光性樹脂等）を侵食したり、剥
離したりする現象が生じる。そのため、従来のめっき液
を使用して銅めっきによる回路形成等を行っても設計通
りに形成することが困難であった。また、そのめっき外
観としても満足できるものが得られなかった。When a copper plating process is performed on a printed wiring board or the like using such a conventional strongly acidic or alkaline plating solution, a resist (photosensitive resin) previously applied to the printed wiring board is used. Etc.) erosion or peeling. For this reason, it has been difficult to form a circuit as designed even if a circuit is formed by copper plating using a conventional plating solution. Also, no satisfactory plating appearance was obtained.
【０００４】さらに、近年のプリント配線板の高密度化
・薄物化傾向により回路の細線化が進み使用されるレジ
スト厚みもさらに薄くなってきたため、従来のめっき液
ではレジスト膨潤・剥離の現象が著しくなりめっき処理
が行えない事態も生じてきた。[0004] Furthermore, due to the recent trend toward higher density and thinner printed circuit boards, circuit thinning has progressed and the resist thickness used has become thinner. Therefore, the phenomenon of resist swelling and peeling has been remarkable with conventional plating solutions. In some cases, plating cannot be performed.
【０００５】そこで、本発明は、従来酸性浴として分類
される硫酸銅の電解銅めっき液を改良し、レジストの膨
潤や剥離を起こすことなくめっきが施せる安定性の高い
電解銅めっき液を提供するとともに予めレジストが塗布
されているプリント配線板等にめっきを施す場合に好適
な電解銅めっき方法を提供せんとするものである。Accordingly, the present invention provides an improved electrolytic copper plating solution of copper sulfate, which is conventionally classified as an acidic bath, and provides a highly stable electrolytic copper plating solution that can be plated without causing swelling or peeling of the resist. It is another object of the present invention to provide an electrolytic copper plating method suitable for plating a printed wiring board or the like to which a resist is applied in advance.
【０００６】[0006]
【課題を解決するための手段】かかる課題を解決するた
め、本発明の電解銅めっき液は、硫酸銅と、ジエチレン
トリアミン五酢酸及び／又はエチレンジアンミン硫酸塩
と、亜硫酸水素ナトリウムと、アンモニア水とを含むも
のとした。このめっき液組成は硫酸銅をベースとしてい
るものであるが、めっき液のｐＨを中性付近で維持する
ことができるので、従来の強酸性又はアルカリ性のめっ
き液で発生するレジストの膨潤や剥離を引き起こすこと
なく銅めっき処理をすることが可能となる。ここにいう
中性付近とはｐＨ５〜１０の範囲を示すものである。In order to solve the above problems, an electrolytic copper plating solution of the present invention comprises copper sulfate, diethylenetriaminepentaacetic acid and / or ethylenediammine sulfate, sodium bisulfite, and aqueous ammonia. Included. This plating solution composition is based on copper sulfate, but since the pH of the plating solution can be maintained near neutrality, the swelling and peeling of the resist generated by the conventional strongly acidic or alkaline plating solution can be prevented. The copper plating can be performed without causing any problem. The term "near neutral" as used herein indicates a range of pH 5 to 10.
【０００７】本発明のめっき液は、硫酸銅を硫酸銅五水
和物として２０〜１００ｇ／ｌ含有し、ジエチレントリ
アミン五酢酸又はエチレンジアミン硫酸塩のいずれか一
方を６０〜１５０ｇ／ｌ含有するか、又はジエチレント
リアミン五酢酸とエチレンジアミン硫酸塩を合わせて６
０〜１５０ｇ／ｌ含有し、そして、亜硫酸水素ナトリウ
ムを１〜２０ｇ／ｌ含有し、さらに３０％アンモニア水
を２０〜２００ｍｌ／ｌ含有することが好ましい。硫酸
銅五水和物で１００ｇ／ｌを越えるとめっき液中に硫酸
銅が溶解しなくなり、２０ｇ／ｌより少ないと電流効率
が悪くなり実用的でない。また、ジエチレントリアミン
五酢酸とエチレンジアミン硫酸塩とは、めっき液に含有
させるアンモニアにより液ｐＨが中性付近となった場合
でも、液中の銅を錯体化し沈殿を防止するものである。
このジエチレントリアミン五酢酸とエチレンジアミン硫
酸塩とはそれぞれ単独で用いることもできるが双方を合
わせて用いてもよい。その際の含有量が６０ｇ／ｌより
少ないと銅の錯体化が完全にされず沈殿物が発生し易く
なり、１５０ｇ／ｌを越えるとヤケめっき状態になるた
め外観が悪くなる。The plating solution of the present invention contains 20 to 100 g / l of copper sulfate as copper sulfate pentahydrate, and contains either 60 to 150 g / l of diethylenetriaminepentaacetic acid or ethylenediamine sulfate, or 6 total of diethylenetriaminepentaacetic acid and ethylenediamine sulfate
It preferably contains 0 to 150 g / l, contains 1 to 20 g / l of sodium bisulfite, and further contains 20 to 200 ml / l of 30% aqueous ammonia. When the amount of copper sulfate pentahydrate exceeds 100 g / l, copper sulfate does not dissolve in the plating solution, and when the amount is less than 20 g / l, the current efficiency deteriorates, which is not practical. Further, diethylenetriaminepentaacetic acid and ethylenediamine sulfate are used to complex copper in the solution and prevent precipitation even when the pH of the solution becomes near neutral due to ammonia contained in the plating solution.
The diethylenetriaminepentaacetic acid and the ethylenediamine sulfate can be used alone or in combination. If the content at that time is less than 60 g / l, the complexation of copper is not completely completed, so that a precipitate is easily generated. If the content exceeds 150 g / l, the appearance becomes poor due to burnt plating.
【０００８】亜硫酸水素ナトリウムは、析出する銅内に
不純物として共析し易い物質を還元する働きをするもの
で、めっき処理における不純物の共析を抑制することが
できる。この亜硫酸水素ナトリウムの含有量は、１ｇ／
ｌより少ないとめっきで得られる銅中に不純物の共析が
多くなり、２０ｇ／ｌを越えるとヤケめっき状態になる
ため外観が悪くなる。この亜硫酸水素ナトリウムは、ジ
エチレントリアミン五酢酸のみの場合やジエチレントリ
アミン五酢酸とエチレンジアミン硫酸塩との両方を含有
する場合は必要であるが、エチレンジアミン硫酸塩のみ
を含有する場合には特に含有しなくてもよい。さらに３
０％アンモニア水の含有量は、２０ｍｌ／ｌより少ない
と液ｐＨが５よりも小さな酸性領域となるためレジスト
の膨潤・剥離を引き起し、２００ｍｌ／ｌを越えると液
ｐＨが１０よりも大きなアルカリ性領域となるため同様
な現象を生じてしまう。[0008] Sodium bisulfite functions to reduce substances which are likely to be eutectoid as impurities in the copper to be precipitated, and can suppress eutectoid deposition of impurities in the plating process. The content of this sodium bisulfite is 1 g /
If the amount is less than 1, the eutectoid content of impurities in the copper obtained by plating will increase, and if it exceeds 20 g / l, the appearance will deteriorate due to burnt plating. This sodium bisulfite is necessary in the case of only diethylenetriaminepentaacetic acid or in the case of containing both diethylenetriaminepentaacetic acid and ethylenediamine sulfate, but may not be particularly contained in the case of containing only ethylenediaminesulfate. . 3 more
If the content of 0% ammonia water is less than 20 ml / l, the solution pH becomes an acidic region smaller than 5, causing swelling and peeling of the resist, and if it exceeds 200 ml / l, the solution pH is greater than 10. A similar phenomenon occurs because of the alkaline region.
【０００９】また、本発明の電解銅めっき液には、ｐＨ
調整剤、錯化剤、界面活性剤を少なくとも１種以上を含
むほうがより好ましい。ｐＨ調整剤としては、アンモニ
ア水、硫酸を使用することができる。このｐＨ調整剤を
適宜添加することにより、めっき処理中に変動するｐＨ
を中性領域（ｐＨ５〜１０）に維持し、レジストの膨潤
や剥離を引き起こさず長時間めっき処理することも可能
となる。錯化剤としては、クエン酸水素２アンモニウム
を用いることができ、好ましくは２０〜９０ｇ／ｌ含有
しておけばめっき液の安定性がさらに向上する。そし
て、界面活性剤は一般的に知られるものを使用できる
が、好ましくはポリエチレングリコールを０．０５〜１
ｇ／ｌ含有させるとピットやボイドの発生が抑制され良
好なめっき外観を得ることができる。The electrolytic copper plating solution of the present invention has a pH
It is more preferable to include at least one or more modifiers, complexing agents, and surfactants. Ammonia water and sulfuric acid can be used as the pH adjuster. By appropriately adding this pH adjuster, the pH that fluctuates during the plating process
Is maintained in a neutral region (pH 5 to 10), and it is possible to perform plating for a long time without causing swelling or peeling of the resist. As the complexing agent, diammonium hydrogen citrate can be used. Preferably, the content of 20 to 90 g / l further improves the stability of the plating solution. As the surfactant, generally known surfactants can be used.
When g / l is contained, generation of pits and voids is suppressed, and a good plating appearance can be obtained.
【００１０】本発明のめっき方法は、上述する電解銅め
っき液を用い、ｐＨ５〜１０、液温２５〜６０℃でめっ
きを施すことを特徴とするものである。ｐＨがこの範囲
を超えるとレジストが膨潤又は剥離等する現象が発生す
るためである。また、液温が２５℃より低いと不純物の
共析が多くなり、６０℃を越えるとめっき液ｐＨの変動
が著しくなるからである。より具体的なめっき条件とし
ては、めっき電流を電流密度１〜７Ａ／ｄｍ2で供給
し、上記の液温、ｐＨ範囲でめっき液を弱撹拌すること
が好ましい。ｐＨはｐＨ調整剤のアンモニア水又は硫酸
を適宜添加することにより調整すればよく、より好まし
くはｐＨ６〜８範囲になるようにコントロールする。The plating method of the present invention is characterized in that plating is performed at a pH of 5 to 10 and a solution temperature of 25 to 60 ° C. using the above-described electrolytic copper plating solution. If the pH exceeds this range, a phenomenon such as swelling or peeling of the resist occurs. If the solution temperature is lower than 25 ° C., eutectoid deposition of impurities increases, and if the solution temperature exceeds 60 ° C., the fluctuation of the plating solution pH becomes remarkable. As more specific plating conditions, it is preferable to supply a plating current at a current density of 1 to 7 A / dm 2 and weakly agitate the plating solution within the above-described solution temperature and pH range. The pH may be adjusted by appropriately adding a pH adjuster such as aqueous ammonia or sulfuric acid, and is more preferably controlled so as to be in the range of 6 to 8.
【００１１】本発明のめっき液を用いてめっき処理する
場合、Ｐｔ／Ｔｉ系等の不溶性アノード或いは溶解性ア
ノードの双方を用いることができる。従来の強酸性硫酸
銅溶液で不溶性アノードを使用した場合、めっき性状を
コントロールするためにめっき液へ添加する有機添加剤
が著しく分解され、めっき液の安定性に欠けるものであ
った。しかし、本発明のめっき液では不溶性アノードを
使用しても有機添加剤の分解はあまり生じないのでめっ
き液の安定性は良く、めっき処理の工程管理も容易に行
うことができる。When plating is performed using the plating solution of the present invention, both a Pt / Ti-based insoluble anode and a soluble anode can be used. When an insoluble anode is used in a conventional strongly acidic copper sulfate solution, an organic additive to be added to a plating solution for controlling plating properties is remarkably decomposed, and the plating solution lacks stability. However, in the plating solution of the present invention, even if an insoluble anode is used, decomposition of the organic additive does not occur so much, so that the plating solution has good stability and the process control of the plating process can be easily performed.
【００１２】[0012]
【発明の実施の形態】本発明の実施形態を実施例１〜６
により具体的に説明する。各実施例のめっき液の組成を
表１に示す。DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described with reference to Examples 1 to 6.
This will be described more specifically. Table 1 shows the composition of the plating solution in each example.
【００１３】[0013]
【表１】 [Table 1]
【００１４】＜表１の説明＞表１中の記号は、次に示す
薬品を表示する。 Ａ：硫酸銅五水和物（ｇ／ｌ） Ｂ：ジエチレントリアミン五酢酸（ｇ／ｌ） Ｃ：エチレンジアミン硫酸塩（ｇ／ｌ） Ｄ：亜硫酸水素ナトリウム（ｇ／ｌ） Ｅ：３０％アンモニア水（ｍｌ／ｌ） Ｆ：クエン酸水素２アンモニウム（ｇ／ｌ） Ｇ：ポリエチレングリコール（ｇ／ｌ）<Explanation of Table 1> The symbols in Table 1 indicate the following chemicals. A: Copper sulfate pentahydrate (g / l) B: diethylenetriaminepentaacetic acid (g / l) C: ethylenediamine sulfate (g / l) D: sodium bisulfite (g / l) E: 30% aqueous ammonia (g / l) F: diammonium hydrogen citrate (g / l) G: polyethylene glycol (g / l)
【００１５】表１で示す各薬品を純水に溶解し、実施例
１〜６の電解銅めっき液を作成した。めっき処理条件
は、液温４５℃で、Ｐｔ／Ｔｉ系の不溶性アノードを用
い電流密度２Ａ／ｄｍ2 のめっき電流を供給して行っ
た。また、めっき処理中は、アンモニア水又は硫酸を適
宜添加することでめっき液ｐＨを７付近で維持し、めっ
き液は弱撹拌し続けた。被めっき対象物はエポキシ樹脂
系積層板表面に回路形成用のレジストが塗布されたもの
で、レジストが塗布されていない部分は無電解銅めっき
により下地層となる銅が処理されたものを用いた。各実
施例のめっき液を用いて、この下地層の銅上に１０μｍ
厚の銅を電析させ回路形成を行った。そして、めっき処
理終了後のレジスト及び形成された銅回路を目視及び顕
微鏡により観察した。Each chemical shown in Table 1 was dissolved in pure water to prepare electrolytic copper plating solutions of Examples 1 to 6. The plating was performed at a liquid temperature of 45 ° C. using a Pt / Ti-based insoluble anode and supplying a plating current having a current density of 2 A / dm 2 . During the plating process, the pH of the plating solution was maintained at around 7 by appropriately adding aqueous ammonia or sulfuric acid, and the plating solution was kept under weak stirring. The object to be plated was one in which a resist for circuit formation was applied to the surface of the epoxy resin-based laminate, and the part where the resist was not applied was one in which copper as an underlayer was treated by electroless copper plating. . Using the plating solution of each example, 10 μm
A circuit was formed by depositing thick copper. Then, the resist after completion of the plating treatment and the formed copper circuit were visually observed and observed with a microscope.
【００１６】また、比較のために、硫酸銅五水和物１５
０ｇ／ｌ、硫酸８０ｇ／ｌ、Ｃｌ-１０ｐｐｍ（ＨＣｌ
で添加）、有機添加剤としてニカワを５ｐｐｍを含む強
酸性銅めっき液[比較例１］と、シアン化銅５０ｇ／
ｌ、シアン化ナトリウム８０ｇ／ｌ、炭酸ナトリウム４
０ｇ／ｌ、水酸化カリウム１５ｇ／ｌを含有するアルカ
リ性銅めっき液[比較例２]とを作成し、両比較例ともに
液温３０℃、電流密度２Ａ／ｄｍ2 のめっき条件で、実
施例と同じ被めっき対象物にめっき処理を行った。For comparison, copper sulfate pentahydrate 15
0 g / l, sulfuric acid 80 g / l, Cl - 10 ppm (HCl
), A strongly acidic copper plating solution containing 5 ppm of glue as an organic additive [Comparative Example 1], and 50 g of copper cyanide /
l, sodium cyanide 80 g / l, sodium carbonate 4
An alkaline copper plating solution [Comparative Example 2] containing 0 g / l and 15 g / l of potassium hydroxide was prepared. In both comparative examples, the plating temperature was 30 ° C. and the current density was 2 A / dm 2. A plating process was performed on the same object to be plated.
【００１７】各実施例及び比較例での観察結果を表２に
示す。Table 2 shows the results of observation in each of the examples and comparative examples.
【００１８】[0018]
【表２】 [Table 2]
【００１９】＜表２の説明＞表２中レジストの膨潤及び
剥離の項目で、無、有、一部有とは以下のことを示す
（表中ボイド、ピットの項目も同じ）。 無：目視及び顕微鏡の観察で確認されなかった。 有：目視により確認された。 一部有：目視では確認できないが、顕微鏡により微小領
域で確認された。また、形成された銅回路の外観項目
で、◎、○、△は次の状態を示す。 ◎：めっき外観が非常に良い。 ○：めっき外観が良好。 △：めっき表面がややくもり気味の状態。<Explanation of Table 2> In the items of swelling and peeling of the resist in Table 2, “none,” “present,” and “partially” indicate the following (the same applies to voids and pits in the table). No: Not confirmed by visual observation or microscopic observation. Existence: It was confirmed visually. Partially present: Although not visible, it was confirmed in a microscopic area by microscopy. In the appearance items of the formed copper circuit, ◎, △, and Δ indicate the following states. A: The plating appearance is very good. ：: Good plating appearance. Δ: The plating surface is slightly cloudy.
【００２０】表２で示すように本実施例１〜６のめっき
液で処理を行っても、プリント基板に予め塗布されたレ
ジストの膨潤や剥離等の現象は生じていなく、得られた
銅回路もピット、ボイドの欠陥が無い上に外観も非常に
良好なものであった。また、クエン酸水素２アンモニウ
ム又はポリエチレングリコールを添加しているめっき液
（実施例５，６）では、より良好な外観を有する銅めっ
きが施せた。As shown in Table 2, even when the treatment was performed with the plating solutions of Examples 1 to 6, the phenomena such as swelling and peeling of the resist previously applied to the printed circuit board did not occur, and the obtained copper circuit was obtained. Also, there were no pits and voids, and the appearance was very good. In addition, with the plating solution to which diammonium hydrogen citrate or polyethylene glycol was added (Examples 5 and 6), copper plating having a better appearance was applied.
【００２１】[0021]
【発明の効果】以上述べたように、本発明の電解銅めっ
き液は硫酸銅をベースとする溶液であるが中性付近の液
ｐＨでめっき処理が可能となるので、プリント配線基板
等の製造工程で使用されるレジストの膨潤や剥離が無
く、良好な銅めっきを施すことができる。また、本発明
のめっき方法によれば、レジストとプリント配線板との
密着性が確保されるため良好なパターンめっきが可能と
なり、さらに、不溶性アノードを使用しても有機添加剤
の分解が少ないため、めっき処理の工程管理も容易とな
る。As described above, the electrolytic copper plating solution of the present invention is a solution based on copper sulfate, but plating can be carried out at a solution pH near neutrality. Good copper plating can be performed without swelling or peeling of the resist used in the process. In addition, according to the plating method of the present invention, good pattern plating becomes possible because the adhesion between the resist and the printed wiring board is ensured, and the decomposition of organic additives is small even when an insoluble anode is used. Also, the process control of the plating process is facilitated.
Claims (6)
００ｇ／ｌと、ジエチレントリアミン五酢酸及び／又は
エチレンジアミン硫酸塩を６０〜１５０ｇ／ｌと、亜硫
酸水素ナトリウムを１〜２０ｇ／ｌと、３０％アンモニ
ア水を２０〜２００ｍｌ／ｌとを含有するものである電
解銅めっき液。1. The method of claim 1 wherein copper sulfate is used as copper sulfate pentahydrate in an amount of 20 to 1%.
00 g / l, 60 to 150 g / l of diethylenetriaminepentaacetic acid and / or ethylenediamine sulfate, 1 to 20 g / l of sodium bisulfite, and 20 to 200 ml / l of 30% aqueous ammonia. Electrolytic copper plating solution.
一種以上を含む請求項１に記載の電解銅めっき液。2. The electrolytic copper plating solution according to claim 1, further comprising one or more of a pH adjuster, a complexing agent, and a surfactant.
酸である請求項２に記載の電解銅めっき液。3. The electrolytic copper plating solution according to claim 2, wherein the pH adjuster is aqueous ammonia and / or sulfuric acid.
ある請求項２又は請求項３に記載の電解銅めっき液。4. The electrolytic copper plating solution according to claim 2, wherein the complexing agent is diammonium hydrogen citrate.
ある請求項２ないし請求項４いずれか１項に記載の電解
銅めっき液。5. The electrolytic copper plating solution according to claim 2, wherein the surfactant is polyethylene glycol.
解銅めっき液を用い、ｐＨ５〜１０、液温２５〜６０℃
でめっきを施すことを特徴とする電解銅めっき方法。6. The electrolytic copper plating solution according to claim 1, wherein the pH is 5 to 10 and the solution temperature is 25 to 60 ° C.
An electrolytic copper plating method characterized in that plating is performed by using.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01846898A JP3737268B2 (en) | 1998-01-30 | 1998-01-30 | Electrolytic copper plating solution and electrolytic copper plating method using the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01846898A JP3737268B2 (en) | 1998-01-30 | 1998-01-30 | Electrolytic copper plating solution and electrolytic copper plating method using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11217689A true JPH11217689A (en) | 1999-08-10 |
| JP3737268B2 JP3737268B2 (en) | 2006-01-18 |
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ID=11972481
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7517555B2 (en) * | 2001-04-27 | 2009-04-14 | Hitachi Metals, Ltd. | Copper plating solution and method for copper plating |
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1998
- 1998-01-30 JP JP01846898A patent/JP3737268B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7517555B2 (en) * | 2001-04-27 | 2009-04-14 | Hitachi Metals, Ltd. | Copper plating solution and method for copper plating |
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| Publication number | Publication date |
|---|---|
| JP3737268B2 (en) | 2006-01-18 |
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